EP2857124B1 - Aqueous slurry for making a powder of hard material - Google Patents

Aqueous slurry for making a powder of hard material Download PDF

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Publication number
EP2857124B1
EP2857124B1 EP14183369.9A EP14183369A EP2857124B1 EP 2857124 B1 EP2857124 B1 EP 2857124B1 EP 14183369 A EP14183369 A EP 14183369A EP 2857124 B1 EP2857124 B1 EP 2857124B1
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Prior art keywords
hard material
powder
weight percent
weight
amount
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German (de)
English (en)
French (fr)
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EP2857124A1 (en
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Pankaj B. Trivedi
Pankaj K. Mehrotra
Neal Myers
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Kennametal Inc
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Kennametal Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B02C17/183—Feeding or discharging devices
    • B02C17/186—Adding fluid, other than for crushing by fluid energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/008—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression characterised by the composition
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C08K3/14—Carbides
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    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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    • B22F2301/15—Nickel or cobalt
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    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
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Definitions

  • the present invention pertains to an aqueous slurry for making a powder of hard material comprising tungsten carbide powder and cobalt powder. More specifically, the present invention pertains to an aqueous slurry for making a powder of hard material such as, for example, a cemented (cobalt) tungsten carbide, and the powder of hard material.
  • the powder of hard material and the article made there from each possess properties that essentially meet properties of a powder of hard material formed from a solvent (i.e. Heptane) -based hard material slurry, as well as the articles made there from, respectively.
  • Cemented carbides e.g., cemented (cobalt) tungsten carbide (WC-Co)
  • WC-Co cemented (cobalt) tungsten carbide
  • Strict and consistent quality control of the cemented (cobalt) tungsten carbide powders used to produce the sintered article is important to achieve products with the desired properties.
  • Solvent-based (e.g., heptane) processing is a common and established technique to produce cemented (cobalt) tungsten carbide powders, but this technique requires rigorous environmental, health, and safety standards because of the risks associated with the flammability and disposal of the solvents.
  • U.S. Patent No. 3,846,126 to Foley et al. discloses the use of water as the solvent and polyvinyl alcohol as the binder.
  • the Foley et al. patent discloses the use of other binders at Col. 3, lines 53-62 wherein these binders include camphor, methyl alcohol, paradichlorobenzene, chloroacetic acid, naphthalene, benzoic acid, phthalic anhydride, glycerine, Acrowax C, ethylene oxide polymers sold as Carbowax, and synthetic gums such as acrylamide and metal stearates.
  • water is the preferred vehicle for milling unless an increase in oxygen content is a concern in which case use of a solvent is sought. When the oxygen content is critical, use of a solvent is the suggested component.
  • Other patent documents are identified and discussed hereinafter.
  • the present invention is an improvement over the most modern practice used today for preparing carbide grade powders. It involves three basic and radical departures from the common practice.
  • U.S. Patent No. 4,886,638 to Penkunas et al. mentions the use of water in the slurry used to make a hard material.
  • U.S. Patent No. 4,902,471 to Penkunas et al. discloses a slurry with an organic additive (see Col. 3, lines 16-17):
  • the organic compound can be an ester of a fatty acid. Some preferred esters are beeswax and carnuba wax. Some preferred fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, and combinations thereof.
  • the first step in forming the grade powder is to combine the binder metal powder with a solid esterified wax to form a first mixture.
  • the preferred waxes are pure beeswax, carnauba wax, candellila wax and combinations of these, although other esterified waxes can be used.
  • U.S. Patent No. 5,922,978 to Carroll discloses the use of deoxygenated water as a liquid component of the slurry with a preferred composition is at Col. 4, lines 10-16:
  • the method comprises mixing, in essentially deoxygenated water, WC powder, Co and the organic binder described above.
  • the WC preferably has a sub- ⁇ m particle size.
  • the Co preferably has a sub- ⁇ m particle size.
  • the organic binder is preferably a paraffin wax. More preferably the organic binder is a paraffin wax provided as an emulsion in water.
  • the Carroll '978 Patent also mentions triethanolamine as a corrosion inhibitor (Col.
  • a corrosion inhibitor such as those known in the art (e.g., corrosion inhibitors useful in the boiler, machining and heat exchanger art), may be used. If added, the corrosion inhibitor should be one that does not, for example, hinder the densification of a part pressed from the pressable powder. Preferably the corrosion inhibitor does not contain an alkali metal, alkaline earth metal, halogen, sulfur or phosphorous. Examples of corrosion inhibitors include those described in U.S. Patent Nos. 3,425,954 ; 3,985,503 ; 4,202,796 ; 5,316,573 ; 4,184,991 ; 3,895,170 and 4,315,889 . Preferred corrosion inhibitors include benzotriazole and triethanolamine. U.S. Patent No. 6,245,288 to Carroll also uses deoxygenated water to avoid oxygen pickup, and also discloses spray drying is the preferred drying method. See Col. 4, lines 60-64.
  • the Kruse patent application discloses a method of making cemented carbide bodies based on tungsten carbide and with a binder phase based on Co or combinations of Co, Ni, and Fe, or Ni and Fe by powder metallurgical methods including wet milling in alcohol or water or a mixture thereof, of powder and pressing agent to form a slurry, drying the slurry to form a granulate by spray drying, pressing the granulate to form bodies of desired shape and dimension and finally sintering.
  • U.S. Patent No. 6,852,274 to Knünz et al. disclose a spray drying process that comprises steps of: forming a sprayable slurry of hard material and metallic binder and water and spraying the slurry without the aid of a water-soluble long chain polyglycol.
  • the parameters for the sprayable slurry are: a sprayable slurry with water as a liquid phase and having a solid particle concentration within a range of 65-85% by weight.
  • the parameters of the spray drying are: a gas inlet temperature of substantially 160° to 220°C and a gas exit temperature in a range of substantially 85° to 130°C, and a ratio of water added with the slurry, in liters per hour, to a tower volume of the spray tower, in m 3 , lies between 0.5 and 1.8 and such that a maximum of 0.17 kg of slurry is atomized per m 3 of incoming drying gas.
  • U.S. Patent No. 6,733,562 to Knünz et al. which has a European counterpart as European Patent No.
  • 1 373 585 B2 discloses a process that calls for the formation of a slurry of a hard material and metal binder and water wherein after formation of the slurry, the process requires the formation of an emulsion of a non-water soluble pressing aid and an emulsifier and water, which is then mixed with the slurry.
  • U.S. Patent No. 6,656,976 to Bergstrom et al. which has European counterpart European Patent No. 1 153 652 B1 , pertains to a well-dispersed slurry of mixture of WC-based and Co-based particles and water wherein one feature is the further component of a dispersant comprising 0.1-10 wt % of a polyethylenimine-based polyelectrolyte.
  • European Patent 1 739 197 B1 discloses using water as the liquid medium along with about 1 to about 3 wt-% of a pressing agent of equal to or less than about 90 wt-% PEG [polyethylene glycol] and equal to or greater than about 10 wt-% of long chain C ⁇ 20 fatty acids, their esters and salts.
  • U.S. Patent No. 6,878,182 to Kruse discloses a method that includes wet milling in water the powders and pressing agent wherein the slurry is formulated to contain 0.02-0.06 wt % of a polyethylenimine-based polyelectrolyte to the cemented carbide slurry containing WC and Co.
  • U.S. Patent No. 7,539,637 B2 to Jutterström et al. pertains to a method of making an agglomerated cemented carbide powder that includes wet milling, preferably in a milling liquid comprising water and/or alcohol or a mixture of water and acetone, a powder mixture containing hard constituent powder(s) and a metallic binder and pressing agents and spray drying the slurry. Before milling, from about 0.05 to about 0.50 wt-% of a complex forming and/or pH-decreasing/increasing additive such as triethanolamine, hydroxides or acids, for example, and a thickener in an amount of thickener from about 0.01 to about 0.10 wt-% is added.
  • a complex forming and/or pH-decreasing/increasing additive such as triethanolamine, hydroxides or acids, for example
  • U.S. Patent No. 7,666,349 B2 to Laarz et al. (European Patent No. 1 806 175 B1 is a counterpart) concerns a method of gel-casting a cemented carbide body.
  • One step in the method is forming an aqueous slurry of WC-Co.
  • the text at Col. 4, lines 22-27 presents a general description: More specifically, the method according to the present invention comprises the forming of a slurry including WC--Co cemented carbide powder and dispersant in an aqueous medium, to which is added a monofunctional monomer, a cross-linker and a suitable initiator for the system. More details about the method are set forth at Col. 4, lines 28-61.
  • U.S. Patent No. 7,285,241 B2 to Puide concerns injection molding or extruding a hard material component.
  • One step in the process is wet milling the raw materials in water, alcohol or a combination thereof, preferably 80 wt % ethanol, and 20 wt % water, together with the ethylene oxide polymer. More details are set forth at Col. 2, line 55 through Col. 3, line 2.
  • U.S. Patent No. 7,303,722 B2 to Bruhn et al. discloses a method to make a hard metal article using powder injection molding or an extrusion method.
  • the method includes a step of wet milling in water or alcohol or a combination of water and alcohol, and the drying the slurry.
  • the text at Col. 3, lines 3-7 provides a basic description of the wet milling:
  • U.S. Patent No. 6,336.951 B1 to Qvick et al. discloses a method of making sub- ⁇ m tungsten carbide tool inserts. The method includes wet milling using ethylalcohol and water as a milling liquid. See Col. 2, lines 23-35.
  • PCT Publication WO98/00256 to Sandvik AB concerns a method of spray drying powder mixtures that includes spray drying cemented carbide slurries consisting of cemented carbide powder containing hard constituents in an alcoholwater solution.
  • the text at page 3, line 31 through page 4, line 28 describes the slurry.
  • European Patent No. 0 963 454 B1 to Sandvik Akiebolag concerns a method of making cemented carbide by powder injection molding.
  • the use of a surfactant in the milling step of the cemented carbide provides for a reduction in the level of the porosity in the sintered part.
  • the surfactant can be a single fatty acid like hexadecanoic acid, tetradecanoic acid, 9,10 Octadecanoic acid, 9,12 Octadienoic acid or 9,12,5 Octadecatrienoic acid mixed with the powder in ethanol, acetone, benzene.
  • the surfactant can be some kind of organometallic compound, Zn-stearate, or corresponding alcohol to a fatty acid such as 1-hexadecanol. It can also be an amine such as octadecylamine. All these surfactants can be milled in ethanol
  • U.S. Patent No. 7,531,022 to Quirmbach et al. which has European counterpart European Patent No. 1 666 616 B1 , discloses a method of using a liquid in the preparation of powder mixtures on the basis of hard metals.
  • the method comprises the steps of: (a) providing a milling liquid comprised of water and an inhibitor wherein the inhibitor being a polyvinyllactam or a mixture of a polyvinyllactam and a wax emulsion; (b) providing a powdered metal comprised of at least one hard metal; (c) combining said liquid with said powdered metal in an attritor to form a moist powder mixture; and (d) atomizing said moist powder mixture in a spray drying installation to produce a powder mixture.
  • United States Published Patent No. US2007/0259970 A1 to Boden et al. pertains to a method for dispersing and passivating particulate powders in water and aqueous media.
  • Water-soluble polyvinylamines and/or the initial products thereof, such as, e.g., polyvinyl formamides, are used for dispersing particulate powders in water and/or aqueous media and furthermore for passivating non-oxidic particulate powders in water.
  • United States Published Patent Application No. US2012/0210822 A1 to Konyashin et al. discloses a method to produce a cemented carbide comprising grains of WC grains, about 3 weight percent to about 20 weight percent binder selected from Co or Co and Ni and grain growth inhibitors.
  • the method includes mixing the powders together by means of a ball mill in a milling medium consisting of hexane with 2 wt% paraffine wax.
  • United States Published Patent Application No. US2005/0132843 A1 concerns a method of making a composite chrome powder generated from a ferrochrome material mixed with a nickel-based material.
  • Acetone or heptane can be added for the step of milling the powder mixture to improve powder distribution during milling.
  • the powder mixture may be combined with deionized water or an organic solvent (e.g. acetone, heptane, etc.) to form a slurry with a certain solid content.
  • Milling for a longer time increases the production costs and essentially reduces the production capacity of a ball mill, as well as increases the amount of iron contamination during the milling using a steel-lined ball mill.
  • a higher content of iron contamination can increase the potential for metallurgical defects in the sintered article..
  • Another drawback with aqueous milling is the potential for the powder to oxidize.
  • an aqueous slurry for making a powder of hard material that does not require a longer milling time in order to achieve the specified powder properties.
  • a reduction in the milling time decreases the production costs and essentially increases the production capacity of a ball mill, as well as decreases the amount of iron contamination during the milling.
  • a lower content of iron contamination can decrease the metallurgical defects (e.g., porosity) in the sintered article.
  • an aqueous slurry for making a powder of hard material that results in powder of a hard material that exhibits an increase in the granule size of the powder batch, achieves narrow granule size distributions, is easier to discharge the powder slurry from the ball mill, and possesses a reduction in the pressing pressure necessary for satisfactory compaction of the powder into the green body which is thought to minimize die wear as well as cracking in the sintered article.
  • the invention is an aqueous slurry useful upon being spray dried for the formation of a powder of hard material comprising tungsten carbide powder and cobalt powder.
  • the aqueous slurry comprises starting powder components of the hard material; an oxidation inhibitor in an amount between 0.2 weight percent and 0.5 weight percent based on active matter content of the weight of the starting powder components of the hard material; a surfactant comprising a polyoxyethylene (5) soyaalkylamine in an amount between 0.05 weight percent and 0.30 weight percent of the weight of the starting powder components of the hard material; a binder in an amount between 1.2 weight percent and 4.0 weight percent of the weight of the starting powder components of the hard material; a defoamer in an amount between 0.05 weight percent and 0.35 weight percent of the weight of the starting powder components of the hard material; and water in an amount between 15 weight percent and 30 weight percent of the weight of the starting powder components of the hard material.
  • the aqueous slurry has a percent solids between 70 percent and 85 percent wherein the percent solids comprises a quotient in percent of the weight of the starting powder components of the hard material divided by the sum of the weight of the starting powder components of the hard material and the weight of the water.
  • the invention is a process for making an aqueous slurry for the formation of a hard material powder comprising the steps of: providing a ball mill; ball milling a mixture of the following: media, starting powder components of the hard material comprising tungsten carbide powder and cobalt powder, an oxidation inhibitor in an amount between 0.2 weight percent and 0.5 weight percent based on active matter content of the weight of the starting powder components of the hard material, a surfactant comprising a polyoxyethylene (5) soyaalkylamine in an amount between 0.05 weight percent and 0.30 weight percent of the weight of the starting powder components of the hard material, a binder in an amount between 1.2 weight percent and 4.0 weight percent of the weight of the starting powder components of the hard material, a defoamer in an amount between 0.05 weight percent and 0.35 weight percent of the weight of the starting powder components of the hard material, and water in an amount between 15 weight percent and 30 weight percent of the weight of the starting powder components of the hard material; and a media:pow
  • the invention is a powder of hard material produced by the process comprising the steps of: spray drying an aqueous slurry comprising: starting powder components of the hard material comprising tungsten carbide powder and cobalt powder; an oxidation inhibitor in an amount between 0.2 weight percent and 0.5 weight percent of the weight of the starting powder components of the hard material; a surfactant comprising a polyoxyethylene (5) soyaalkylamine in an amount between 0.05 weight percent and 0.30 weight percent of the weight of the starting powder components of the hard material; a binder in an amount between 1.2 weight percent and 4.0 weight percent of the weight of the starting powder components of the hard material; a defoamer in an amount between 0.05 weight percent and 0.35 weight percent of the weight of the starting powder components of the hard material; and water in an amount between 15 weight percent and 30 weight percent of the weight of the starting powder components of the hard material.
  • the aqueous slurry has a percent solids between 70 percent and 85 percent wherein the percent solids comprises a quotient in percent of the weight of the starting powder components of the hard material divided by the sum of the weight of the starting powder components of the hard material and the weight of the water, wherein the granule size distribution of the powder of hard material is D 10 - 67.8 ⁇ m, D 50 - 115.8 ⁇ m and D 90 - 169.9 ⁇ m.
  • the present invention pertains to an aqueous slurry for making a powder of hard material comprising tungsten carbide powder and cobalt powder. More specifically, the present invention pertains to an aqueous slurry for making a powder of hard material such as a cemented (cobalt) tungsten carbide, and the powder of hard material.
  • the powder of hard material and the article made there from each possess properties that essentially meet properties of a powder of hard material formed from a solvent-based hard material slurry, as well as the articles made there from, respectively.
  • the specific powder grade that results from this process is a cemented (cobalt) tungsten carbide powder that is of a composition of between about 93 weight percent and about 94 weight percent tungsten carbide and between about 6 weight percent and about 7 weight percent cobalt.
  • the initial step comprises adding deionized water (DI Water) and milling media and alkylpolyalkyleneglycolether, which in this specific embodiment is available under the name Contraspum K1012 from Zschimmer & Schwarz GmbH & Co. KG in Langstein, GERMANY to a steel-lined ball mill, and then stirring this mixture in the steel-lined ball mill for about 1 minute.
  • DI Water deionized water
  • the content of the alkylpolyalkyleneglycolether is in weight percent of the total powder components.
  • the media comprises 5 millimeter (mm) cycloids that comprise a cemented (cobalt) tungsten carbide that is of a composition that comprises about 94 weight percent tungsten carbide and about 6 weight percent cobalt.
  • the actual amounts of the components, as well as the media:powder ratio i.e., the quotient of the weight of the media (e.g., cemented (cobalt) tungsten carbide cycloids) divided by the total weight of the powder components
  • the media:powder ratio i.e., the quotient of the weight of the media (e.g., cemented (cobalt) tungsten carbide cycloids) divided by the total weight of the powder components
  • the second step comprises adding a mixture of amines and vinyl polymers in an aqueous solution to the post-stirred mixture of the first step that is in the steel-lined ball mill.
  • the mixture of aqueous amines and vinyl polymers is available under the name Product KM1508 from Zschimmer & Schwarz GmbH & Co. KG in Langstein, GERMANY, which according to the product brochure is an oxidation inhibitor for aqueous preparation of hard metals.
  • the content of the mixture of the aqueous amines and vinyl polymers (or the volume of aqueous amines as referred to below when using METAMAX I-15) as based on 100 percent active matter content is in weight percent of the total powder components.
  • a volume of aqueous amines can be an alternative for the mixture of amines and vinyl polymers in an aqueous solution.
  • aqueous amines are available under the name METAMAX I-15 from Zschimmer & Schwarz GmbH & Co. KG in Langstein, GERMANY, which according to the product brochure is an oxidation inhibitor for aqueous preparation of hard metals.
  • mixture of amines and vinyl polymers in an aqueous solution e.g., Product KM1508
  • the volume of aqueous amines e.g., METAMAX I-15
  • Table A below sets forth some of the properties of Product KM1508 and METAMAX I-15 as taken from the product brochures.
  • Table A Properties of Product KM1508 and METAMAX I-15 Material/Property Product KM1508 METAMAX I-15 appearance clear, slightly yellowish, viscous liquid clear-turbid, colourless liquid solubility in water soluble in any proportion unrestrictedly soluble density approx. 1.07 g/cm 3 approx. 1.05 g/cm 3 water content not reported approx. 88% active matter approx. 28% not reported
  • the third step comprises adding a wax dispersant to the post-stirred mixture of the second step in the steel-lined ball mill, and then stirring (or ball milling) the new mixture in the steel-lined ball mill for a pre-selected time depending upon the powder batch size and the powder grade.
  • the content of the wax dispersant is in weight percent of the total powder components.
  • the wax dispersant is available under the name METAMAX B-4 from Zschimmer & Schwarz GmbH & Co. KG in Langstein, GERMANY, which according to the product brochure is a wax dispersion useful as a binding and pressing agent. Table B below sets forth some of the properties of METAMAX B-4 as taken from the product brochures.
  • the fourth step comprises adding the powder components to the post-stirred mixture of the third step, and then stirring (or ball milling) the new mixture in the steel-lined ball mill for a pre-selected time dependent upon the powder batch size and the powder grade.
  • the powders comprise only the tungsten carbide powder and the cobalt powder.
  • the particle size of the starting powders (tungsten carbide powder and cobalt powder) can range between sub- ⁇ m (less than 1 ⁇ m) to about 50 ⁇ m.
  • the fifth step comprises adding polyoxyethylene (5) soyaalkylamines, which has application as a surfactant, to the post-ball milled mixture of the fourth step in the steel-lined ball mill.
  • the polyoxyethylene (5) soyaalkylamine is available under the name "Ethomeen” from ZZ Amsterdam, The Netherlands. Table C below sets forth some properties of the Ethomeen S/15 product.
  • the content of the polyoxyethylene (5) soyaalkylamine e.g., Ethomeen
  • the content of the polyoxyethylene (5) soyaalkylamine is in weight percent of the total powder components.
  • the content of the polyoxyethylene (5) soyaalkylamine can vary from 0.05 weight percent to 0.30 weight percent of the total starting powder components.
  • the content of the polyoxyethylene (5) soyaalkylamine can range between 0.05 weight percent 0.20 weight percent of the total starting powder components.
  • Ethomeen is available in a number of different grades and there is the contemplation that each one of the grades of Ethomeen will function in a satisfactory fashion.
  • the mixture After adding the polyoxyethylene (5) soyaalkylamines, which typically takes place between about 15 minutes to about 30 minutes before the slurry is ready for discharge from the ball mill, the mixture is and then stirred (or ball milling) in the steel-lined ball mill for a pre-selected time dependent upon the powder batch size and the powder grade. The result is the production of an aqueous slurry.
  • the sixth step comprises discharging the aqueous slurry after the milling per the fifth step into a metal container.
  • the seventh step is to sieve the discharged mixture of the sixth step through about 200 mesh screen.
  • the eighth step comprises transferring the sieved slurry of the seventh step to a feed tank.
  • the ninth step comprises adding DI (deionized) water to the ball mill to recover additional powder, and then spray drying the slurry to achieve a dry powder with specific properties. Ranges for the spray drying parameters are as follows:
  • the tenth step comprises pressing the sprayed powder into a green body.
  • the eleventh step comprises vacuum sintering the green body into a sintered article at a peak temperature between 2500°F (1371°C) and 2900°F (1593°C) for a duration at peak temperature between 30 minutes and 120 minutes.
  • One specific sintering parameter used in the examples is a vacuum sinter at a temperature equal to about 2825 °F (1551.6°C) for a duration equal to about 45 minutes.
  • the following specific properties can be measured: magnetic saturation, coercive force, hardness, density, porosity, and microstructure.
  • the initial step comprises adding: • deionized water (DI Water) in the amount of 1250 grams (25 wt.% of the total powder components which equals 5000 grams) • media (5 mm cycloids comprising WC(94 wt%)-Co(6 wt%) wherein the cycloids have a weight of either 21,000 grams (for a media:powder ratio equal to 4.2) or 30,000 grams (for a media:powder ratio equal to 6.0) • alkylpolyalkyleneglycolether (i.e., Contraspum K1012 which is a defoamer) in the amount of 10 grams
  • the second step comprises: • adding a mixture of amines and vinyl polymers in an aqueous solution (i.e., Product KM1508 which is an oxidation inhibitor) in the amount of 50 grams (0.28 wt% based on active matter content of the total powder components) • with the option of adding Meta
  • the total weight of the powder components is 5000 grams with the tungsten carbide powder comprising 4700 grams and the cobalt powder comprising 300 grams. • 8-10 hours ball milling
  • the fifth step comprises adding: • polyoxyethylene (5) soyaalkylamines which is available under the name "Ethomeen", which is a surfactant • there were four different amounts relating to the "Ethomeen®” content, and they were: • no "Ethomeen” (0 weight percent of the total powder components) • 3.75 grams of "Ethomeen” (0.075 weight percent of the total powder components) • 7.50 grams of "Ethomeen” (0.15 weight percent of the total powder components) • 12.5 grams of "Ethomeen” (0.25 weight percent of the total powder components)
  • the eleventh step comprises
  • FIG. 1 comprises a graph that reports the average granule size in ⁇ m for each of three groupings of powder.
  • Each powder grade comprises about 94 weight percent tungsten carbide and about 6 weight percent cobalt.
  • the compositions shown by the clear bars (i.e., without lining) did not use Ethomeen.
  • Granule size distributions of the powder batches are represented as D 10 , D 50 and D 90 , where D 50 is the median granule size that splits the granule size distribution with half above and half below this size; 90% of granules fall below D 90 size and 10% of granules are smaller than D 10 size..
  • the powder batch that did not use Ethomeen average D 10 is 7.0 ⁇ m, D 50 is 106.0 ⁇ m and D 90 is 159.0 ⁇ m.
  • the average D 10 is 67.8 ⁇ m, D 50 is 115.8 ⁇ m and D 90 is 169.9 ⁇ m.
  • FIG. 1 shows results that reflect about a 20% increase in the average granule size with the use of "Ethomeen” in the processing of the powders. Further, the powder batches that used "Ethomeen” had a narrow size distribution.
  • FIG. 2 is a bar chart that reports the counts of the pores (that have a size greater than 25 ⁇ m per unit area) in the sintered article.
  • the technique used to determine the counts for the porosity was ASTM B276 - 05(2010) "Standard Test Method for Apparent Porosity in Cemented Carbides".
  • the microstructural defects of porosity can play an important role in the fracture initiation, and therefore, there is a need to control the content of porosity to avoid premature failure of the sintered article.
  • pressure-sinter operations may reduce the number of pores in the microstructure, such operations add cost to the overall process. As the results below demonstrate, the present invention reduces the porosity in vacuum sintered material without the need to pressure-sinter the article.
  • Ethomeen is synonymous with the scientific term polyoxyethylene (5) soyaalkylamine. There is no intention to limit the scope by the use of "Ethomeen” instead of polyoxyethylene (5) soyaalkylamine.
  • the media:powder ratio was equal to 4.2, the inhibitor was Metamax I-15, and the process did not use "Ethomeen”.
  • the media:powder ratio was equal to 4.2, the inhibitor was KM1508, and the process did not use "Ethomeen”.
  • the media:powder ratio was equal to 6.0, the inhibitor was Metamax I-15, and the process did not use "Ethomeen”.
  • the media:powder ratio was equal to 6.0, the inhibitor was KM1508, and the process did not use "Ethomeen”.
  • Table 1 reports the data that is shown in FIG. 2 .
  • the M&P # in Table 1 corresponds to the Powder Batch number in FIG. 2 per the Table E below.
  • Table E Correspondence between Table 1 and FIG. 2 Table 1
  • FIG. 2 CT2331274 1 CT2331901 2 CT2034326 3 CT2531119 4 CT2454375 5 CT2454373 6
  • the technique used to determine the counts for the porosity was ASTM B276 - 05(2010). All of the data reported in FIG. 3 were from a sintered article made via a process in which the media:powder ratio was equal to 6.0.
  • the composition of the article is about 94 weight percent tungsten carbide (coarse grain) and about 6 weight percent cobalt.
  • the data points that are in the form of squares comprise the results from a sintered article made via a process that did not use "Ethomeen” and did not use KM1508 as an inhibitor.
  • the data point that is in the form of a circle comprises the results from a sintered article made via a process that did not use "Ethomeen", but did use KM 1508 as an inhibitor.
  • the data points that are in the form of a triangle comprise the results from a sintered article that used "Ethomeen” and also used the inhibitor KM 1508. It becomes apparent from the data reported in FIG. 3 that the use of "Ethomeen” and the inhibitor KM 1508 reduced the number of pores (that have a size greater than 25 ⁇ m per unit area) in the sintered articles.
  • Ethomeen polyoxyethylene (5) soyaalkylamine
  • the KM1508 inhibitor may contain a green-strength additive that can contribute to the drop in the number of pores (that have a size greater than 25 ⁇ m per unit area). It also appears that the use of Ethomeen helps with the dispersion of wax, typically used in this process, and subsequently makes the de-binding process during sintering more effective.
  • Table 2 reports the data that is shown in FIG. 3 .
  • the M&P # in Table 2 corresponds to the Powder Batch number in FIG. 3 per the Table F below.
  • Table F - Correspondence between Table 2 and FIG. 3 Table 2 FIG. 3 CT2631119 1 CT2454375 2 CT2454373 3 CT2474995 1 CT2531271 2 CT2536520 3
  • this bar chart reports the pressing pressure for six powder batches that have a composition that comprised about 94 weight percent tungsten carbide and about 6 weight percent cobalt, (or processing parameters).
  • the powder batch represented by the bar with lining was produced without using "Ethomeen”.
  • the powder batches represented by the clear bars (without lining) were produced by a process using "Ethomeen”.
  • the 1.2 Die Factor pressing pressure was reduced by about 8 percent in the WC-Co coarse grain powder when 0.15 weight percent Ethomeen (polyoxyethylene (5) soyaalkylamine) was used in the aqueous slurry.
  • the 1.2 Die Factor pressing pressure was reduced by about 25 percent in the WC-Co coarse grain powder when 0.25 weight percent Ethomeen (polyoxyethylene (5) soyaalkylamine) was used in the aqueous slurry.
  • Ethomeen polyoxyethylene (5) soyaalkylamine
  • DF Die Factor
  • the drop in the 1.2 Die Factor pressing pressure could be due to an increase in the Scott density, which provides better powder packing characteristics. This provides a benefit in that higher pressing pressures can lead to cracks in the sintered articles and also cause excessive wear on the dies.
  • Table 3 reports the data that is shown in FIG. 4 .
  • the M&P # in Table 3 corresponds to the Powder Batch number in FIG. 4 per the Table G below.
  • Table G - Correspondence between Table 3 and FIG. 4 Table 3
  • FIG. 4 CT2454373 1 CT2474995 2 CT2531271 3 CT2536520 4 CT2613645 5 CT2613868 6
  • this bar chart reports the milling time for six powder batches that have a composition that comprised about 94 weight percent tungsten carbide and about 6 weight percent cobalt.
  • the bars with lining represent the results from a process wherein the media:powder ratio was equal to 4.2 and the clear bars represent the results from a process wherein the media:powder ratio was equal to 6.0.
  • KM 1508 was used as an inhibitor.
  • Metamax I-15 was used as inhibitor. The results reported in FIG.
  • Table 4 reports the data that is shown in FIG. 5 and in FIG. 6 .
  • the M&P # in Table 4 corresponds to the Powder Batch number in FIGS. 5 and 6 per the Table H below.
  • Table H - Correspondence between Table 4 and FIGS. 5 and 6 Table 4 FIGS. 5 & 6 CT2034326 1 CT2454373 2 CT2331274 3 CT2331901 4 CT2531119 5 CT2454375 6
  • the lined bar represents a powder batch processed with the media: powder ratio equal to 4.2 and the clear bars represent a powder batches processed using a process with the media: powder ratio equal to 6.0.
  • FIG. 6 show that the iron (Fe %) contamination dropped from 1.58% after 34 hours of milling to 0.39% after 10 hours when using the Metamax I-15 and 0.28% after 10 hours of milling when using the KM 1508 inhibitor.
  • the results reported in FIG. 6 show that the higher media:powder ratio results in a reduction of the iron contamination.
  • Table 4 reports the data that is shown in FIG. 7 .
  • the M&P # in Table 4 corresponds to the Powder Batch number in FIG. 7 per the Table I below.
  • Table I - Correspondence between Table 4 and FIG. 7 Table 4 FIG. 7 CT2331901 4 CT2531119 5 CT2454375 6
  • this chart provides a summary of benefits by using a higher media: powder ratio, "Ethomeen” and KM 1508 on pores (size greater than 25 ⁇ m per unit area).
  • KM1508 contains green strength additive. It shows that best results are obtained (i.e. zero porosity) using a higher media: powder ratio, KM1508 and "Ethomeen”.
  • Table 1 Effect of edia powder ratio on poroosity count (that have size groater than 25 microns por unit area) MLP* Inhibitor Surfactant Binder Defoamer Milling Time (hrs) Media : Powder parasity count Type wt % Type wt. % Type wt. % Type wt.
  • Ethomeen drops the pressing pressure for the powder batch material. A reduction in the pressing pressure necessary for satisfactory compaction of the powder into the green body is thought to minimize die wear as well as cracking in the sintered article.
  • the use of a higher media:powder ratio reduces the milling time necessary to achieve the specified powder properties. A reduction in the milling time reduces production costs and can increase production capacity without adding additional equipment.
  • the high media:powder ratio also results in a reduction of the iron contamination (Fe%) during the milling. Lower iron contamination during the milling minimizes metallurgical defects in the sintered article.
  • Ethomeen increases the granule size of the powder batch and results in the production of powder batches with narrow granule size distributions. These are advantageous properties for the powder batch material since the granule size of the cemented carbide controls powder flow, pressing pressure and sintering response.
  • Ethomeen also facilitates with the powder slurry discharge from the ball mill. This is an advantageous property for the efficient production of the powder batch material since it saves processing time and improves powder yield.

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EP14183369.9A 2013-10-03 2014-09-03 Aqueous slurry for making a powder of hard material Active EP2857124B1 (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108883467B (zh) * 2016-04-15 2021-02-02 山特维克知识产权股份有限公司 金属陶瓷或硬质合金的三维打印
CN110229989B (zh) * 2019-05-09 2021-04-23 陕西理工大学 一种多元硬质合金及其制备方法
US11691155B2 (en) * 2020-09-17 2023-07-04 U.S. Silica Company Methods and apparatus for producing nanometer scale particles utilizing an electrosterically stabilized slurry in a media mill
CN114985746A (zh) * 2022-06-09 2022-09-02 四川一然新材料科技有限公司 一种超细硬质合金粉末喷雾干燥制粒方法
WO2024006659A1 (en) * 2022-06-29 2024-01-04 Locus Solutions Ipco, Llc Grinding aid compositions and methods of use

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425954A (en) 1966-01-24 1969-02-04 Cromwell Paper Co Four component multipurpose corrosion inhibitor
JPS5327694B2 (zh) 1972-02-05 1978-08-10
US3846126A (en) 1973-01-15 1974-11-05 Cabot Corp Powder metallurgy production of high performance alloys
US3888662A (en) 1973-02-09 1975-06-10 Kennametal Inc Method of centrifugally compacting granular material using a destructible mold
US3985503A (en) 1975-03-17 1976-10-12 The Sherwin-Williams Company Process for inhibiting metal corrosion
US4070184A (en) 1976-09-24 1978-01-24 Gte Sylvania Incorporated Process for producing refractory carbide grade powder
US4184991A (en) 1978-03-13 1980-01-22 Zimmite Corporation Corrosion inhibiting composition for ferrous metals and method of treating with same
US4202796A (en) 1978-07-31 1980-05-13 Chemed Corporation Anti-corrosion composition
US4315889A (en) 1979-12-26 1982-02-16 Ashland Oil, Inc. Method of reducing leaching of cobalt from metal working tools containing tungsten carbide particles bonded by cobalt
USRE34180E (en) 1981-03-27 1993-02-16 Kennametal Inc. Preferentially binder enriched cemented carbide bodies and method of manufacture
US4610931A (en) 1981-03-27 1986-09-09 Kennametal Inc. Preferentially binder enriched cemented carbide bodies and method of manufacture
US4397889A (en) 1982-04-05 1983-08-09 Gte Products Corporation Process for producing refractory powder
US4478888A (en) 1982-04-05 1984-10-23 Gte Products Corporation Process for producing refractory powder
US4886638A (en) 1989-07-24 1989-12-12 Gte Products Corporation Method for producing metal carbide grade powders
US4902471A (en) 1989-09-11 1990-02-20 Gte Products Corporation Method for producing metal carbide grade powders
US5007957A (en) 1990-09-10 1991-04-16 Gte Products Corporation Method for producing tungsten carbide grade powders suitable for isostatic compaction
US5045277A (en) 1990-09-10 1991-09-03 Gte Products Corporation Method of producing metal carbide grade powders and controlling the shrinkage of articles made therefrom
US5316573A (en) 1992-03-12 1994-05-31 International Business Machines Corporation Corrosion inhibition with CU-BTA
US5641920A (en) * 1995-09-07 1997-06-24 Thermat Precision Technology, Inc. Powder and binder systems for use in powder molding
WO1998000257A1 (en) 1996-06-28 1998-01-08 Sandvik Ab (Publ) Method of making powder mixtures
SE9603936D0 (sv) 1996-10-25 1996-10-25 Sandvik Ab Method of making cemented carbide by metal injection molding
SE518885C2 (sv) 1998-02-20 2002-12-03 Seco Tools Ab Sätt att tillverka skär i submikron hårdmetall
US5922978A (en) 1998-03-27 1999-07-13 Omg Americas, Inc. Method of preparing pressable powders of a transition metal carbide, iron group metal or mixtures thereof
US7539637B2 (en) 1998-04-24 2009-05-26 Starmine Corporation Security analyst estimates performance viewing system and method
US6245288B1 (en) 1999-03-26 2001-06-12 Omg Americas, Inc. Method of preparing pressable powders of a transition metal carbide, iron group metal of mixtures thereof
SE516324C2 (sv) 2000-05-09 2001-12-17 Sandvik Ab Framställning av väldispergerade suspensioner lämpliga för spraytorkning
AT4928U1 (de) 2001-03-29 2002-01-25 Plansee Tizit Ag Verfahren zur herstellung eines hartmetallansatzes
AT4929U1 (de) 2001-03-29 2002-01-25 Plansee Tizit Ag Verfahren zur herstellung von hartmetallgranulat
SE522462C2 (sv) 2001-12-19 2004-02-10 Seco Tools Ab Metod att tillverka hårdmetallkroppar innefattande bildande av en slurry och en slurry
EP1440956A1 (en) 2003-01-24 2004-07-28 Seco Tools Ab Method of making tungsten carbide based hard materials
SE526575C2 (sv) 2003-08-27 2005-10-11 Seco Tools Ab Metod att tillverka en sintrad kropp
SE526194C2 (sv) 2003-08-27 2005-07-26 Seco Tools Ab Metod för att tillverka en sintrad kropp
US20050132843A1 (en) 2003-12-22 2005-06-23 Xiangyang Jiang Chrome composite materials
DE102004020559A1 (de) 2004-04-27 2005-12-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Dispergierung und Passivierung von feinteiligen Pulvern in Wassern und wässrigen Medien
SE0401644D0 (sv) * 2004-06-23 2004-06-23 Hoeganaes Ab Lubricants for insulated soft magnetic iron-based powder compositions
DE102004053221B3 (de) 2004-11-04 2006-02-02 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Flüssigkeit und deren Verwendung zur Aufbereitung von Hartmetallen
SE529202C2 (sv) 2005-05-17 2007-05-29 Sandvik Intellectual Property Sätt att tillverka en agglomererad pulverblandning av en slurry och agglomererat pulver
SE529705C2 (sv) 2005-06-27 2007-10-30 Sandvik Intellectual Property Sätt att tillverka en pulverblandning för hårdmetall
SE529370C2 (sv) 2006-01-09 2007-07-17 Sandvik Intellectual Property Vattenbaserad hårdmetallslurry, gelad hårdmetallkropp och sätt att framställa en gelad kropp och en sintrad hårdmetallkropp
US20100107509A1 (en) * 2008-11-04 2010-05-06 Guiselin Olivier L Coated abrasive article for polishing or lapping applications and system and method for producing the same.
GB0919857D0 (en) 2009-11-13 2009-12-30 Element Six Holding Gmbh Near-nano cemented carbides and process for production thereof
JP5544928B2 (ja) * 2010-02-26 2014-07-09 セイコーエプソン株式会社 造粒粉末および造粒粉末の製造方法
JP5544945B2 (ja) * 2010-03-11 2014-07-09 セイコーエプソン株式会社 造粒粉末および造粒粉末の製造方法
EP2377506B1 (en) * 2010-04-16 2014-08-13 Ivoclar Vivadent AG Composite ceramic material comprising zirconia

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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US9475945B2 (en) 2016-10-25
US20170001916A1 (en) 2017-01-05
JP2015071828A (ja) 2015-04-16
US20150096467A1 (en) 2015-04-09
CN104511588A (zh) 2015-04-15
EP2857124A1 (en) 2015-04-08
US9796633B2 (en) 2017-10-24
KR20150039682A (ko) 2015-04-13
IL234943A0 (en) 2014-12-31

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